Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/928—Polyolefin fiber

Definitions

• the present invention relates to novel metal derivatives of N,N'-dialkyl esters of ethylenedinitrilo tetraacetic acid and the use thereof in the preparation of synthetic polymeric compositions of increased stability to ultraviolet (UV) light and increased susceptibility to dye.
• UV ultraviolet
• this invention relates to a compound of the formula:
• R is an alkyl group of from 1 to 22 carbon atoms
• M is selected from the group consisting of zinc, manganese, nickel, cobalt, chromium, copper, aluminum, titanium and iron, and n has a value of from 1 to 4, the value of n being the same as the available valence of M.
• alkyl is intended a branched or straight chain saturated hydrocarbon group having from 1 to 22 carbon atoms.
• Typical of such alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, isopentyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl and the like.
• the group n consists of a metal cation such as the cation form of lithium, sodium, potassium, barium, cal cium, aluminum, titanium, tin, vanadium, antimony, chromium, molybdenum, manganese, iron, cobalt, copper and the like, that is, a metal having an atomic number of up to 6.
• the preferred metal cations are zinc, manganese, nickel, cobalt, chromium, copper, aluminum, titanium and iron. The most preferred is nickel.
• compositions of matter which are stabilized against ultraviolet deterioration which comprises a synthetic organic polymer normally subject to ultraviolet deterioration containing from about 0.05% to by weight of the polymer of the compounds of Formula 1 and preferably from 0.2% to 5% by weight.
• the compounds of the present invention also render synthetic polymeric substances, such as the polya-olefins of the polyethylene and polypropylene type, more amenable to dyeing and also reduce the tendency of the polymeric substance to discolor and embrittle upon exposure to light, whether dyed or not.
• synthetic polymeric substances such as the polya-olefins of the polyethylene and polypropylene type
• These compounds may be incorporated in the polymeric substance during the usual processing operations, for example by hot milling, the
• compositions containing these novel salts may be dyed, either directly after incorporation of the salt or after further processing, such as the formation of yarns or fabrics.
• the polymer is stabilized by the presence of these metal salts both before and after dyeing so that the coloring step need not follow directly.
• the colored compositions exhibit fastness to light and to solvents, properties preferred in washing, dry cleaning and general use.
• the conditions of the dyeing will of course vary with the particular dye employed. Generally the nature of the dye is not restricted and any of the many known metal chelating dyes may be employed, as for example, the orange dye of the formula:
• the effect obtained with a particular dye can be altered by variation of the particular metal cation of these compounds and by the amount of these compounds present in the polymer, although generally from about 0.05 to 10% preferably 0.1 to 5% by weight, is employed.
• Materials for which the compounds of the present invention are useful thus include synthetic organic polymeris substances, both homopolymeric and copolymeric, such as vinyl resins formed from the polymerization of vinyl halides or from the copolymerization of vinyl halides with unsaturated polymerizable compounds, e.g., vinyl ester, a,fi-unsaturated acids, a,B-unsaturated esters, refiunsaturated ketones, a,fiunsaturated aldehydes and unsaturated hydrocarbons such as butadienes and styrene; poly-a-olefins such as polyethylene, polypropylene, polybutylene, polyisoprene and the like, including copolymers of poly-a-olefins; polyurethanes such as are prepared from
• lubricating oil of the aliphatic ester type e.g., di-(Z-ethylhexyl) azelate, pentaerythritol tetracaproate and the like
• animal and vegetable derived oils e.g., linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, cotton seed oil and the like
• hydrocarbon material such as gasoline, both natural and synthetic, diesel oil, mineral oil, fuel oil, cutting fluids, waxes, resins and the like
• fatty acids varnishes, soaps; and the like.
• the stabilizers employed in this invention can be also used in combination with other stabilizers or additives.
• compounds which help to improve the heat and oxidative stability of polymers such as phenolic compounds which inactivate free radicals, by hydrogen atom donation, as well as, compounds capable of decomposing peroxides such as dilaurylthiodipropionate.
• the stabilizers may also be used in combination with other additives such as UV light absorbers, anti-acids such as calcium soaps, phosphates, anti-static agents, and the like.
• Other materials which may also be incorporated into the polymer composition include for example, pigments, dyes, fillers, etc.
• the stabilized polymers of the present invention have utility in the normal uses for which plastics are employed and are particularly useful for film, coatings and fiber.
• the compounds of the present invention per se, can be prepared by treating the appropriate dialkyl ester of ethylenedinitrilotetraacetic acid with the reactive form of the metal or complex, e.g., sodium hydroxide, lithium hydroxide, potassium hydroxide or the like.
• the reactive form of the metal or complex e.g., sodium hydroxide, lithium hydroxide, potassium hydroxide or the like.
• a double decomposition is employed.
• a sodium salt of the present invention is treated with nickel chloride.
• use of other halides such as aluminum chloride, barium chloride and the like results in formation of the corresponding metal derivative.
• N,N'-dialkyl esters of ethylenedinitrilotetraacetic acid that are used as starting materials in preparing the compounds of this invention are described in US. Pat. No. 3,497,535.
• the N,N-dialkyl esters of ethylenedinitrilotetraacetic acid can conveniently be prepared by the reaction of ethylenedinitrilotetraacetic acid dianhydride and suitable alcohols.
• reaction mixture was then clarified by filtration, the clear filtrate being concentrated by distillation at 45 C. and 15 mm. mercury.
• the isolated residue was dissolved in 100 ml. of benzene, filtered, and the residue isolated by distillation of the solvent at 4045 C. at a pressure of 0.10 mm. Hg for 3 hours.
• Nickel complex of N,N'-dimethyl ester of ethylenedinitrilotetraacetic acid (b) Nickel complex of N,N'-di-n-buty1 ester of ethylenedinitrilotetraacetic acid (c) Nickel complex of N,N'-di-n-dodecyl ester of ethylenedinitrilotetraacetic acid.
• EXAMPLE 4.--LIGHT STABILIZATION TESTS Outdoor exposure tests (a) Sample preparation: 5 mil oriented monofilaments. The nickel complex of di-n-octadecyl ester of ethylenedinitrilo tetraacetic acid was dissolved in distilled methylene chloride and blended with polypropylene (Hercules Profax 6501) in a Hobart mixer. A buffer (such as calcium stearate) and antioxidant (di-octadecyl (3,5-di-tbutyl-4-hydroxybenzyl) phosphonate) were added to the polymer blend. To facilitate moisture removal all blends are vacuum dried shortly before extrusion. Samples were also prepared containing the additional UV stabilizer (2- (3,5-di-t-butyl- -hydroxyphenyl)-5'-chlorobenzotriazole.
• Sample preparation 25 mil plaques.Unstabilized polypropylene powder (Hercules Profax 6501) is thoroughly blended with the indicated amounts of additives. The blended material is then milled on a two roll mill for 5 minutes at 182. The milled sheet is then compression molded at 220 C. into 25 mil thick plaques under a pressure of 175 p.s.i. and water cooled in the press.
• Unstabilized polypropylene powder Hercules Profax 6501
• the blended material is then milled on a two roll mill for 5 minutes at 182.
• the milled sheet is then compression molded at 220 C. into 25 mil thick plaques under a pressure of 175 p.s.i. and water cooled in the press.
• EXAMPLE 6 A composition comprising acrylonitrile-butadienestyrene terpolymer and 1% by weight of the nickel complex of di-n-octadecyl ester of ethylenedinitrilotetraacetic acid resists embrittlement due to UV deterioration longer than one which does not contain the stabilizer.
• a composition comprising polyurethane and 1.0% by weight of the tin complex of di-n-dodecyl ester of ethylenedinitrilo tetraacetic acid is more stable under fluorescent sunlamps, black lights and fluorescent lights than the uniormulated polyurethane.
• EXAMPLE 7 A stabilized linear polyethylene is prepared by incorporating therein 0.5% by Weight of the aluminum complex of di-n-octadecyl ester of ethylenedinitrilotetraacetic acid.
• a stabilized polyamide (nylon 6,6) is prepared by incorporating therein 0.1% of chromium complex of din-dodecyl ester of ethylene diamine tetraacetic acid.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (8)

Cited By (3)

Families Citing this family (3)

• 1971
  • 1971-08-30 US US00176307A patent/US3751440A/en not_active Expired - Lifetime
• 1972
  • 1972-07-19 CA CA147,446A patent/CA984849A/en not_active Expired
  • 1972-08-22 GB GB3911172A patent/GB1399368A/en not_active Expired
  • 1972-08-23 JP JP47084428A patent/JPS4832930A/ja active Pending
  • 1972-08-28 DE DE2242189A patent/DE2242189A1/de active Pending
  • 1972-08-29 IT IT28595/72A patent/IT964344B/it active
  • 1972-08-30 FR FR7230759A patent/FR2152001A5/fr not_active Expired
  • 1972-08-30 NL NL7211817A patent/NL7211817A/xx unknown

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